Separation of olefins from paraffins



United States Patent SEPARATION OF OLEFINS FROM PARAFFINS David W. Peck, Charleston, Robert R. Gentry, St. Albans, and Henry E. Fritz, Charleston,.W. Va., assignors to Union Carbide Corporation, a corporation of New York', 4 No Drawing. Filed Mar. 31, 1964, Ser. No. 356,070 Claims. (Cl. 260-666) This invention relates to a method for the separation of olefinic hydrocarbons from saturated "hydrocarbons. More particularly, this invention relates to a liquid-phase separation of olefins from paraffins employing molecular sieves; v

Although it is well known that molecular sieves can be employed to separate hydrocarbon compounds on the basis of their degree ofunsaturation, none of the known of olefin-free product, aproduct stream significantly en- ,richedin olefin content cannot be obtained. Moreover, the main effect of the sieve is to isomerize the olefins.

,Finally, Milton ,has" indicated in U.S. Patents: 3,078,636 and 3,078,644 that the separating ability of the sieves is lost when the hydrocarbon stream is liquid. e 'Jthas been discovered by this'invention, however, that when hydrocarbon fractionsare contacted in the liquid phase with a molecular sieve having a pore size sufficientlylarge to adsorb benzene, a highly efiicientfand practical process is obtained, Unexpectedly. and surprisingly, in addition to permitting good separations at commercially feasible rates, little or no isomerization of olefins results.

The molecularsievesemployed in the process of this invention are those well known to those skilled in the art, and are those at least partially dehydrated molecular sieves having substantially uniform pore sizes sufliciently large to adsorb benzene, generally at least about .7 Aug.

stroms in diameter. As examples of sieves or this type, one can mention the zeolite X type sieve as disclosed and claimed in U.S. Patent 2,882,244 to Miltonhaving pore sizes in the range of about8 to about 10 Angstronis, the" zeolite Y-type' sieve as disclosed in U.S. Patent No.

3,130,007, issuedApril 21,1964, and the zeoliteL type sieve as disclosed in U.S. application Serial No. 122,398 filed June 7, 1961, by D. W. Breek and N. A. Acara, and now abandoned. If desired, the molecular sieves may be treated by variousjmethods .to inhibit polymerization, such as treatment with an amine as disclosed inBelgian Patent 608,439. However, such treatments ordinarily are unnecessary when conductinga liquid-phase separation in accordance withthis invention.

The feed employed in the process of this invention can be anyhydrocarbon fraction containing at least two components, one of which has a higher degree of olefinic unsaturation'than the other. For example, the feed can consistfiot n-olefins and n-parafiins, branchedolefins and 3,265,759 Patented August 9, 1966 "ice branched paraffins, cycle-olefins and cycloparafiins, alkenyl aromatic compounds and alkylaromatic compounds, as well as mixtures of one or more of the foregoing classes, and the like.

The process of this invention is especially suitable for separating hydrocarbons of three different classes. The first class comprises hydrocarbons containing olefinic double bonds which are not desirably isomerized, for example, an alpha-olefin of from 4 to 20 carbon atoms or a diolefin. The second class comprises acylic hydro-.

carbons of from about 10 to about 20 carbon atoms, and the third class comprises hydrocarbons of up to about 20 carbons containing at least one cyclic moiety, i.e., alloy- 1 tion by distillation.

clic compounds and compounds containing an aromatic ringgboth of which cannot be readily separated by the known processes. I

The temperature at which 'the process of this invention is conducted is not highly critical, provided the separation is effected under conditions at which the feed is liquid. Thus, temperatures of from about 10 C. or lower 1 up to the boiling point of the liquid being separated under the conditions of the separation are readily employed. As the temperature is increased, however, the degree of selectivity is adversely affected somewhat, and, accordingly, temperatures below about C. are preferred, with temperatures of about room temperature (20 to 25 C.) being particularly preferred.

The pressure under which the process of this invention is conducted is not highly critical and atmospheric, sub

exceeds the desired level, the feed to the bed is stopped and the desorption cycle is begun. Instead of stationary beds, one can employ moving beds or fluid beds of molecular sieves. In addition, several beds may be employed in parallel to provide for a substantially continuous' overall opera-tion.

Desorption ofv the sieve bed may be effected by any of several techniques. For example, one can drain the bed of unadsorbed hydrocarbons and then wash the bed with a highly polar mate-rial, such as water, ethers, alcohols and the like. A preferred technique comprises flushing thelbed with a low boiling liquid parafiin, then flushing pa-raflln. In each case the low boiling material should have a normal boiling point at least 30 C. below that of the hydrocarbon being separated to permit easy separa- Preferred materials are olefins or parafi'ins of from 4 to about 7 carbons, such as butene, butane, pentene, pentane, heptene, heptene, and the like. The first paraifin wash removes unadsorbed hydrocarbon from the sieve bed, and the low boilingolefinic compound is employed to desorb the olefins from the sieve which are then washed from the bed with the low boiling para-ffin. The use of low boiling mate-rials for this purpose, particularly for the first parafiin wash, is considered unusual in view of the disclosure of C. I. Egan in U.S. 3,054,838 that low molecular weight materials are more from the bed. gwere recovered 4 grams of 91% n-undecenes. i

strongly adsorbed in the liquid phase than high molecular weight materials on SA type sieves.

The sieve bed is reactivated by known methods, such as heating to elevated temperatures or subjectingit to low pressures. Reactivation is ordinarily unnecessary when the preferred technique outlined above is employed to free the bed of adsorbed olefins. However, after several cycles, it may be necessary to heat the bed to remove the polymers and other adsorbed material.

The following examples are illustrative. In the examples, the conditions are room temperature and, pressure unless otherwise specified.

Example I An 80-grarn sample of n-undecane containing 5 weight percent-C random n-olefins (i.e., a mixture of n-undecene isomers) wasv charged to the top of a column packed wit-h 200 grams of 12-30 mesh 13X molecular sieve manufactured by the Linde Division of Union Carbide Corporation. Then pentane was charged to the sieve to wash unadsorbed hydrocarbons from the bed, which were recovered in two fractions. After evaporation of the pentane, each fraction was weighed and analyzed for olefin content by bromine addition. The first fraction weighed 64 grams and contained less than 0.1% olefin and the second fraction weighed 9 grams and containedonly 1% olefin. Butene-l was then charged to the column to free adsorbed olefins and then pentane was charged to the column to wash the desorbed olefins After evaporation of the pentane, there Example 2 I I T'S'O 'gram' portion of n-dodecene-l in n dodec wa's' ciharg'ed to'thetop of a column containing400- rantees 1 2 m'shflBX molecular s'ievew 'llhe sieve? was lien charged with 500millilit'ersofpentane to remove theii-do'decane and 'tlushed with lbutene vapors to free adsorbedl-dodecene' The-freed l-dodecene was washed from the sieve with pentane and the eflluent was evaporated to recover 15 grams of 99% l-dodecene. The sieve bed was then charged with a second ISO-gram portion of the dodecane-dodecene mixture and there were recovered 13 grams of 96% l-dodecene in the manner described above. This procedure was repeated two additional times to obtain 15 grams of 99% l-dodecene and 14 grams of 97% l-dodecene.

Example 3 A rni xture of straight chain C -C parafiins and. ran-v dorn olefins containing 9.3% olefins was pumped upward. 1 inch by,."52;ineh glass column packed. with 4 1 2 gra ns of 12'- mesh 13X molecular sieve at a ratejof1,160milliliters per hour and the effluent was collected in'20-milliliter fractions. The first 340 milliliters (260 grams) contained less than 0.2% olefin. Olefin breakthrough then became significant and pumping of the olefin-paraffin mixture was continued until the olefin content of the effluent was equal to that of the feed, at which point the total volume pumped was 1,500 milliliters. The column was then drained and 500 milliliters of pentane were poured down through the sieve to wash off unadsorbed parafiin. A 400-milliliter portion of ethyl ether was charged to the column to free adsorbed olefin from the sieve. After evaporation of the ether from the efinent, there were recovered 24 grams of 99% olefins.

Example 4 A solution of 10 grams of C -C alpha-n-olefins in 90 grams of C -C n-parafiins was charged to the top ofa -millimeter diameter column packed with 450 grams of 13X molecular sieve powder which had been treated to exchange the normally present sodium ions by potassium ions. Pentane was then added to the top of the bed to wash out unadsorbed hydrocarbons and the. resultant efiluent was taken in three fractions from which the pentane was distilled. Then methanol was added to the top of the sieve to elute the adsorbed olefin and the. methanolic etlluent was distilled to remove methanol. Each of the four fractions thus obtained was analyzed by bromine addition, and the percent olefin in each cut was calculated based on an average molecular weight of 200 for the mixed olefin. The results of the analyses of the four fractions are set forth in tabular form below:

Percent Olefin Cut No. Weight Example 5 Employing apparatus and procedure similar to those described in Example 4, a ZOO-gram sample of C -C n-paraflins and random n-olefins containing 9% olefins was charged to the top of a column containing 400 grams of potassium-exchanged 13X molecular sieve powder. Pentane was added to elute the parafiins, which were recovered in four fractions, and then methanol was added to elute the olefins. After distillation of the solvents from the dive fractions, the fractions were analyzed by bromine addition, and the olefin content of each was calculated based on an average molecular weight of 168 for the o1efins. The results of these analyses are set forth in tabular formbelow:

Percent Olefin Got No. Wt. Grams Example 6 desorb the olefins, which were then washed from the sieve with pentane. 0n evaporation of the pentane from the effluent there were obtained 6.8 grams of 91% olefins.

Example 7 Employing apparatus and procedures similar to those described in Example 4, 500 grams of the olefin-paraffin mixture employed in Example 5 were charged to the top of a column containing 350 grams of potassium-exchanged 13X sieve. There were recovered from the bottom of the column 228 grams of paraflin containing 0.1% olefins. Pentane was charged to the column to wash out unadsorbed paraffin and olefin. The last 5 grams of the hydrocarbon eluted by the pentane was combined with 10 grams of olefins freed by flooding the sieve with butene-l followed by washing the sieve with pentane. The combined product contained 94% olefins.

Example 8 An -gram sample of 10% l-dodecene in n-dodecane was charged to the top of a 1-inch ID. column packed with 200 grams of 12-30 mesh potassium-exchanged 13X r '1 6 molecular sieve. The hydrocar bon was eluted with 460- decene, and the next 8 grams consisted of 98.6 percent milliliters of pentane, the effluent was collected in f'racdecane. The olefin content of the eflluent then increased tions and the pentane was distilled off. There were rerapidly to approach the feed composition, and, after 187 covered 46 grams of n-dodecane containing 0.1% l-dograms had been fed to the column, the feed was termidecene and 27 grams of an olefin-paraflin mixture contain nated. The column was drained, heated to 250 C. and ing 15% l-dodecene. The sieve bed was flushed with washed with 300 milliliters of pentane. The resulting butene-l, then pentane, and, after evaporation of solvent effluent was recovered in two fractions which, after refrom the effluent, therewere obtained 4 grams of 97% moval of pentane, weighed 18 grams and 4 grams, rel-dodecene. spectively, and contained 84 percent and 77 percent dec- The sieve was reactivated by subjection to reduced 10 cane, respectively, as determined by bromine number. pressure (12 millimeters absolute) to remove residual The decene present in these fractions had partly isombutene-l' and pentane. The reactivated sieve was then erized to internal decenes as determined by infrared analyemployed to separate a 40-gram sample of the dodecenesis. The column was cooled to room temperature and dodecane mixture and then reactivated in the manner dewashed with 700 milliliters of ethyl ether to recover adscribed above. The sieve was. again charged with a 40- 15- sorbed decene. The adsorbate, after evaporation of the gram sample of the dodecene-dodecane mixture and'eluted ether, weighed 7 grams and contained only 44 percent with 200 milliliters of pentane to give 33 grams of ndoof mixed n-decene isomers. decane containing 0.5% l-dodecene and 3 grams contain- A comparison of this example with Example 3 illusing 18% olefins. On treatment of the sieve with butened trates the necessity for conducting the separation of C and then pentane there were recovered 4 grams of 83 20 and higher aliphatic hydrocarbons in the liquid phase. l-d'odecene. Thus, although olefin-free paraffin could be recovered Example 9 with vapor-phase operation, the amount of 99% paraffin Was only 0.1 gram per gram of sieve bed, whereas A total of 400 grams of 12% l'dodeoelle in n'diodwane' the amount of 99.8+% parafiin: recovered in Example was charged t0 thfi P of a 9911mm containing g 3 was over 0.63 gram per gram of sieve bed. Similarly, of 12-30 mesh 13X molecular which had been in this example only 0.035 gram of 44% olefin per gram with silver Pitrate sdlrutivn exchange sodi' of sieve bed was recovered, whereas 0.057 gram of 99 10115 Silver 10115 and adv/Med y 1162111112 at percent olefin was recovered per gram of sieve bed in l 5C. Thefi'rst 127 grams of efliuent from the column con- Example 3 f l tained no l-dodecene as determined by vaporphase 3 0 Example 1 t chromatography. After the sieve was drained, it was v i washed. with 600 milliliters. of pentane. The eolumnwas A 400-sram'm1Xwre of l-dodecene m ec then washed with butene-l and then pentane to obtain w fed to a bed of 400 grams f 14- 0 mesh 5A mo- 20 grams f 9 14 lecular sieve. The first 26 grams of efiiuent were only l 1,0 95 dodecane. After draining unabsorbed-liquid, the Exampe bed was flushed with 400 milliliters of ethylbenzene and Employing procedures similar to those described in then 400 milliliters of l-hexad'ecene to desorb the do- Example 9, a 400-gram sample of 10% n-dodecene in ndecene. The resulting eflluent contained dodecene and dodecane was fed to a bed of200 gramsof 10X powdered dodecane in approximately the same ratio as the feed. molecular sieve. There were recovered 125 grams of 40 E l 15 99.7% n-dodecane and 6.5 gramsgof 94% n-dodecene. mm? 9 E le 11 A 200-gram mixture of 10% n-dodecene in n-dodecane was charged to a column of 200 grams of 5A molecular sieve. The first 100 grams of effluent were 92.3 per- 5. cent dodecane. After washing the bed with one liter of benzene to remove non-adsorbed C hydrocarbons, the bed was washed with one liter of pentane to displace ad- A 46-gram mixture of 21% cyclodedecene and 78% cyclododecane was dissolved in 54' grams of pentane and fed' to a bed containing 200 grams of 12-30 mesh 13X molecular sieve. The bed was then flushed with pentane and! after evaporation of pentane there were sorbed dodecene. After evaporation of pentane from ered: 31' grams of 97% cyclododecane. The bed was then 1 flushed with butene-l vapors followered by a. p ntane gg fgig fi glf there'weremwverd 25 grams wash After revaporauon 0f butene and pemane from the These last two examples illustrate that small-pore size resultant emuent there were recovered 7 grams of 10% sieves, such as a 5A sieve, will not efiectively separate cyclododecene' long-chain olefins and paraffins in the liquid phase. Al Example though a slightly enriched paraflin efiluent can be re- Av mixture of 25 grams of styrene and 1-00 gramsof 55 covered, it is recovered in substantially smaller quanethy-lbenzene was fed to a bed containing. 400 grams of tities than: when a larger-pore size sieve is employed. For '12-30 mesh 13X molecular sieve. The bed was flushed example, only 0.065 gram of 95% dodecane was rewith 700 milliliters of pentane to recover, after evaporacovered per gram of 5A sieve in Example 14, whereas tion of the pentane, 30 grams of ethyl-benzene containing. over 0.57 gram of 100% dodecane was recovered per no styrene as determinedby vaporphase chromatography. gram of 13X sieve in Example 9 and over 0.62 gram The bed was then washed with 400 milliliters oi benzene of 99.7% dodecane was recovered per gram of 10X sieve followed by 300 milliliters of pentane to recover, after in Example 10. Moreover, the olefin adsorbate, which in evaporation of benzene and pentane, 42 grams. of 77 Examples 9 and 10 was 94' to 98 percent olefin, was percent ethylbenzene. Finally, the bed was washed with not significantly difierent from the. feed composition in ethyl ether to remove adsorbed styrene and, after'evapora- 5 1 Examples 14 and 15.

tion of ethyl ether from the effluent, there were recovered What is claimed is: 11 grams of 89 percent styrene. 1. The method for separating an olefinically-unsatu- Example 13 rated hydrocarbon from a mixtureqcontaining said unsaturated hydrocarbon and a more saturated hydroear- A miXwfe 0f Percent l'decene d 1 bon which comprises the steps of (l) contacting said n-decauo W s Continuously fed to the of a column mixture in the liquid. phase. with a bed of an at least Packed with 200 gTamS 0f pfltassium-exchaflged-i 1' partially dehydrated molecular sieve having a substanmesh 13X molecular sieve which was heated at 200 tially uniform pore size of dimensions sufficient to per- C. to maintain the feed in the vapor phase. The. first mit. benzene to pass into the pores thereof, (2.). there- 13 grams of eflluent consisted of decane containing no after contacting said sieve containing adsorbed. olefin.-

7 ically-unsaturated hydrocarbon with a parafiin having a boiling point at least 30 C. below that of the unadsorbed hydrocarbon to remove unadsorbed hydrocarbons from said bed, and (3) desorbing the adsorbed hydrocarbon from said sieve bed by contacting said sieve bed with a polar liquid.

2. The process as claimed in claim 1 wherein said olefinically-unsaturated hydrocarbon is an m-olefin of from 4 to 20 carbons, inclusive.

3. The process as claimed in claim 1 wherein said olefinically-unsaturated hydrocarbon and said more saturated hydrocarbon each contain at least one cyclic moiety and contain not more than 20 carbons.

4. The process as claimed in claim 1 wherein said olefinically-unsaturated hydrocarbon is styrene and said more saturated hydrocarbon is ethylbenzene.

5. The process as claimed in claim 1 wherein said olefinically-unsaturated and more saturated hydrocarbons are acyclic hydrocarbons of from to 20 carbons, inclusive.

6. The method for separating an olefinically-unsaturated hydrocarbon from a mixture containing said unsaturated hydrocarbon and a more saturated hydrocarbon which comprises the steps of 1) contacting said mixture in the liquid phase with a bed of an at least partially dehydrated molecular sieve having a substantially uniform pore size of dimensions suflicient to permit benzene to pass into the pores thereof, (2) flushing the bed with a parafiin having a boiling point at least 30 C. below that of said mixture to remove unadsorbed hydrocarbons, (3) contacting said sieve containing ad sorbed olefinically-unsaturated hydrocarbon with an olefin having a boiling point at least 30 C. below that of the adsorbed hydrocarbon, (4) and thereafter flushing said bed with a parafiin having a boiling point at least 30 C. below that of said olefinic hydrocarbon to remove said olefinic hydrocarbon and said olefin. I

7. The process as claimed in claim 6 wherein said olefinically-unsaturated hydrocarbon is an a-olefin of from 4 to 20 carbons, inclusive.

8. The process as claimed in claim 6 wherein said olefinically-unsaturated hydrocarbon and said more saturated hydrocarbon each contain at least one cyclic moiety and contain not more than 20 carbons.

9. The process as claimed in claim 6 wherein said olefinically-unsaturated hydrocarbon is styrene and said more saturated hydrocarbon is ethylbenzene.

10. The process as claimed in claim 6 wherein said olefinically-unsaturated and more saturated hydrocarbons are acyclic hydrocarbons of from 10 to 20 carbons, inclusive.

References Cited by the Examiner UNITED STATES PATENTS 2,882,243 4/1959 Milton 260-676 2,971,993 2/1961 Kimberlin et al 260-676 2,988,503 6/1961 Milton et al. 260-666 3,054,838 9/ 1962 Egan 260-676 3,094,483 6/1963 Hengstebeck 260-676 3,182,017 5/1965 Fleck et al. 260-666 3,207,803 9/1965 Davis 260-676 DELBERT E. GANTZ, Primary Examiner. V. OKEEFE, Assistant Examiner. 

1. THE METHOD FOR SEPARATING AN OLEFINICALLY-UNSATURATED HYDROCARBON FROM A MIXTURE CONTAINING SAID UNSATURATED HYDROCARBON AND A MORE SATURATED HYDROCARBON WHICH COMPRISES THE STEPS OF (1) CONTAINING SAID MIXTURE IN THE LIQUID PHASE WITH A BED OF AN AT LEAST PARTIALLY DEHYDRATED MOLECULAR SIEVE HAVING A SUBSTANTIALLY UNIFORM PORE SIZE OF DIMENSIONS SUFFICIENT TO PERMIT BENZENE TO PASS INTO THE PORES THEREOF, (2) THEREAFTER CONTACTING SAID SIEVE CONTAINING ADSORBED OLEFINICALLY-UNSATURATED HYDROCARBON WITH A PARAFFIN HAVING A BOILING POINT AT LEAST 30*C. BELOW THAT OF THE UNADSORBED HYDROCARBON TO REMOVE UNADSORBED HYDROCARBONS FROM SAID BED, AND (3) DESORBING THE ADSORBED HYDROCARBON FROM SAID SIEVE BED BY CONTACTING SAID SIEVE BED WITH A POLAR LIQUID. 